Fluorine-containing hydrocarbon composition

ABSTRACT

A fluorine-containing hydrocarbon composition comprising the following (1) and (2), wherein the proportions of (1) and (2) in the composition are such that (1) is 100 parts by weight, and (2) is from 0.001 to 10 parts by weight: 
     (1) at least one pentafluoropropane selected from 1,1,1,3,3-pentafluoropropane and 1,1,2,2,3-pentafluoropropane, 
     (2) the following (i) or (ii): 
     (i) a combination of (a) and at least one member selected from the following (b) to (e): 
     (a) a compound having --NO 2 , 
     (b) a compound having --CN, 
     (c) a compound having --CONR 1  R 2  wherein each of R 1  and R 2  which are independent of each other, is a hydrogen atom or an alkyl group, 
     (d) a lactone, 
     (e) a quinone, 
     (ii) at least one member selected from the following (f) and (g): 
     (f) a reaction product of a compound having a halogen atom and an epoxy group with an active hydrogen compound, 
     (g) a reaction product of a compound having a halogen atom and a hydroxyl group with an isocyanate compound.

This application is a Division of application Ser. No. 08/925,145, filedon Sep. 8, 1997.

The present invention relates to a fluorine-containing hydrocarboncomposition containing "at least one pentafluoropropane selected from1,1,1,3,3-pentafluoropropane (R245fa) and 1,1,2,2,3-pentafluoropropane(R245ca)" (hereinafter sometimes referred to simply as apentafluoropropane).

Heretofore, 1,1-dichloro-1-fluoroethane (R141b) or1,1,1,-trifluoro-2,2,-dichloroethane (R123) has been used as asubstitute for trichlorofluoromethane (R11), for e.g. a blowing agentfor preparation of a polyurethane foam (a polyurethane blowing agent), arefrigerant for a centrifugal chiller or a solvent for cleaning.

However, it has already been decided by Montreal protocol that ahydrochlorofluorocarbon such as R141b or R123 will be totally banned inthe year 2020, since its adverse effect to the ozone layer is not zeroalthough it is small as compared with a chlorofluorocarbon such as R11.Accordingly, it is of urgent necessity to develop a substitute material.As a substitute material for R141b or R123, R245fa or R245ca which is ahydrofluorocarbon, is considered to be a prospective candidate compound.

R245fa or R245ca is excellent in stability. However, when variouscompounds are coexistent, or when it is contacted with equipmentmaterials, its stability tends to deteriorate, and various decompositionproducts are likely to be formed.

For example, in its application as a solvent, an alcohol is usuallyadded to increase the dissolving power, and at the same time, it will becontacted with the cleaning machine or with the material to be cleaned,and a stain component such as oil, or moisture will be included.Further, in its application as a propellant, an alcohol will be addedfor the purpose of dissolving a water-soluble effective component, andat the same time, it will be contacted with the container material. Inits application as a polyurethane blowing agent, a polyol as a startingmaterial for polyurethane, a catalyst, a foam stabilizer, etc. will becoexistent, and it will-be contacted with a blowing machine. Further,when it is used as a refrigerant for e.g. a centrifugal chiller, it willbe contacted with the material constituting the chiller or with alubricant oil.

When decomposition of a pentafluoropropane occurs, for example, in acase of an aerosol product, there will be problem such as an odor orcoloring of the liquid due to an oxidized product of the alcohol, orcorrosion of the container due to a hydrogen halide formed as adecomposition product.

Further, in polyurethane foaming, there will be a problem such as adecrease in the foaming degree due to deactivation of the catalyst, anincrease of the viscosity of the polyol starting material, or yellowingof the product. In the case of a chiller, there will be a problem suchas corrosion of the machine due to a hydrogen halide formed as adecomposition product, or a machine trouble due to deterioration of thelubricant oil.

JP-A-5-239251 discloses a nitro compound, a benzophenone, or the like asa stabilizer for a R245fa blowing agent. However, the stabilizerdisclosed in this publication does not necessarily provide an adequatestabilizing effect.

It is an object of the present invention to provide a composition whichis capable of effectively stabilizing a pentafluoropropane, particularlycapable of effectively controlling formation of decomposition productsof a pentafluoropropane, such as 1,3,3,3-tetrafluoropropene (R1234ze),1,2,3,3-tetrafluoropropene (R1234ye), 1,1,1,3-tetrafluoropropane(R254fb) and 1,2,2,3-tetrafluoropropane (R254ca).

The present invention provides a fluorine-containing hydrocarboncomposition comprising the following (1) and (2), wherein theproportions of (1) and (2) in the composition are such that (1) is 100parts by weight, and (2) is from 0.001 to 10 parts by weight:

(1) at least one pentafluoropropane selected from1,1,1,3,3-pentafluoropropane and 1,1,2,2,3-pentafluoropropane,

(2) the following (i) or (ii):

(i) a combination of (a) and at least one member selected from thefollowing (b) to (e);

(a) a compound having --NO₂,

(b) a compound having --CN,

(c) a compound having --CONR¹ R² wherein each of R¹ and R² which areindependent of each other, is a hydrogen atom or an alkyl group,

(d) a lactone,

(e) a quinone,

(ii) at least one member selected from the following (f) and (g):

(f) a reaction product of a compound having a halogen atom and an epoxygroup with an active hydrogen compound,

(g) a reaction product of a compound having a halogen atom and ahydroxyl group with an isocyanate compound.

Now, the present invention will be described in detail with reference tothe preferred embodiments.

According to the composition of the present invention, thepentafluoropropane can be stabilized by incorporating the specificcompound. Particularly, it is possible to suppress formation of itsdecomposition products such as R1234ze, R1234ye, R254fb and R254ca.R1234ze and R254fb are decomposition products of R245fa. R1234ye andR254ca are decomposition products of R245ca.

(a) may, for example, be a nitroalkane such as nitromethane ornitroethane, or an aromatic nitro compound such as nitrobenzene,p-nitrotoluene, 2,4-dinitrobenzene, 3,4-dinitrobenzene,1,3-dinitrotoluene or 1,2-dinitrotoluene.

(b) may, for example, be an aliphatic nitrile such as acetonitrile, oran aromatic nitrile such as benzonitrile, p-methylbenzonitrile orm-methylbenzonitrile.

(c) may, for example, be a formamide such as N,N-dimethylformamide orN,N-diethylformamide, or an acetamide such as N,N-dimethylacetamide,N,N-diethylacetamide or N-methylacetanilide. The carbon number of thealkyl group R¹ or R² is preferably from 1 to 5.

(d) may, for example, be a β-lactone, a γ-lactone or a δ-lactone.Preferred is β-propiolactone, β,β-dimethyl-β-propiolactone,γ-butyrolactone, γ-valerolactone, γ-caprylolactone, γ-crotolactone,δ-valerolactone or δ-caprolactone.

(e) may, for example, be p-benzoquinone, o-benzoquinone,9,10-anthraquinone or 1,4-naphthoquinone.

In (f), the compound having a halogen atom and an epoxy group, may, forexample, be an aliphatic hydrocarbon having a halogen atom and an epoxygroup, an alicyclic hydrocarbon having a halogen atom and an epoxygroup, or an aromatic hydrocarbon having a halogen atom and an epoxygroup. Preferred is an aliphatic hydrocarbon having a halogen atom andan epoxy group. Epichlorohydrin (EPCH) is particularly preferred as thealiphatic hydrocarbon having a halogen atom and an epoxy group.

In (f), the halogen atom is preferably one selected from a chlorineatom, a bromine atom and an iodine atom. Particularly preferred is achlorine atom. A plurality of halogen atoms are preferably ones selectedfrom chlorine atoms, bromine atoms and iodine atoms. Particularlypreferred are a plurality of halogen atoms consisting solely of chlorineatoms.

In (f), the active hydrogen compound is a compound having at least oneactive hydrogen-containing group selected from e.g. an alcoholichydroxyl group, a phenolic hydroxyl group, a primary amino group, asecondary amino group and a carboxyl group.

The active hydrogen compound may have two or more activehydrogen-containing groups. Further, the active hydrogen compound mayhave one active hydrogen-containing group, but is preferably a compoundhaving two or more active hydrogen-containing groups.

The active hydrogen compound may, preferably, be a monool, a polyol, analkanolamine or a phenol.

The monool may, for example, be a monool such as methanol, ethanol,propanol or butanol. The polyol may, for example, be a polyol such asglycerol, sucrose, ethylene glycol, propylene glycol,trimethylolpropane, pentaerythritol, dextrose, methylglycoside orsorbitol.

The alkanolamine may, for example, be ethanolamine or diethanolamine(DEAM).

The phenol may have various substituents such as an alkyl group, analkenyl group, an alkoxy group, a carboxyl group and a carbonyl group,in addition to the hydroxyl group.

The phenol may, for example, be a monophenol such as2,6-di-t-butyl-p-cresol, o-cresol, m-cresol, p-cresol, thymol,p-t-butylphenol, o-methoxyphenol, m-methoxyphenol, p-methoxyphenol,eugenol, isoeugenol, butylhydroxyanisole, phenol or xylenol, or apolyphenol such as bisphenol A, bisphenol F, t-butylcatechol,2,5-di-t-amylhydroquinone, 2,5-di-t-butylhydroquinone, m-pyrocatechol,4-chlorocatechol, 4-bromocatechol, 3,4-dihydroxytoluene,3,4-dioxybenzophenone, 3,4-dioxyacetophenone, p-t-butylpyrocatechol,pyrogallol, resol (a derivative of phenol) or benzilic type polyol (aderivative of phenol).

Further, a polyol having an alkylene oxide such as ethylene oxide (EO)or propylene oxide (PO) added to the above active hydrogen compound, oran active hydrogen compound such as a hydroxyl-terminated prepolymerhaving an isocyanate reacted in an amount of at most the equivalentamount to such a polyol, is also preferred.

(f) is preferably a halogen-containing polyether polyol. Thehalogen-containing polyether polyol is preferably an aliphatichydrocarbon having a halogen atom and an epoxy group, particularly areaction product of epichlorohydrin with an active hydrogen compound.The halogen of the halogen-containing polyether polyol is preferablycontained in the form of a halogenated alkyl group.

In (g), the compound having a halogen atom and a hydroxyl group may, forexample, be an aliphatic hydrocarbon having a halogen atom and ahydroxyl group, an alicyclic hydrocarbon having a halogen atom and ahydroxyl group, or an aromatic hydrocarbon having a halogen atom and ahydroxyl group. Preferred is an aliphatic hydrocarbon having a halogenatom and a hydroxyl group, such as ethylene chlorohydrin, α-propylenechlorohydrin, β-propylene chlorohydrin, trimethylene chlorohydrin,tetramethylene chlorohydrin, glycerol-α-monochlorohydrin,glycerol-β-monochlorohydrin, glycerol-α,β-dichlorohydrin orglycerol-α,γ-dichlorohydrin.

In (g), the halogen atom is preferably selected from a chlorine atom, abromine atom and an iodine atom. Particularly preferred is a chlorineatom. A plurality of halogen atoms are preferably ones selected fromchlorine atoms, bromine atoms and iodine atoms. Particularly preferredare a plurality of halogen atoms consisting solely of chlorine atoms. Asan example wherein the halogen atom is a bromine atom, propylenebromohydrin (PBH) may, for example, be mentioned.

As the compound having a halogen atom and a hydroxyl group, a reactionproduct of the above-mentioned compound having a halogen atom and anepoxy group in (f) with an active hydrogen compound, is also preferred.Particularly preferred is a halogen-containing polyether polyol obtainedby reacting an aliphatic hydrocarbon having a halogen atom and an epoxygroup, such as epichlorohydrin, to an active hydrogen compound as aninitiator.

(g) is a compound having a urethane bond which is obtainable by reactinga hydroxyl group in a compound having a hydrogen atom and a hydroxylgroup with an isocyanate group in an isocyanate compound. This reactionproduct may be a compound which has an unreacted hydroxyl group or anunreacted isocyanate group, and has a urethane bond. Further, thisreaction product is preferably selected to have a molecular weight sothat it is soluble in the pentafluoropropane.

(g) is preferably a reaction product of the above-mentionedhalogen-containing polyether polyol with an isocyanate compound. Thisreaction product is preferred, since it is excellent in stability in amixed state with a polyol and a blowing agent.

The isocyanate compound may be an aromatic, alicyclic or aliphaticpolyisocyanate having at least one isocyanate group, preferably at leasttwo isocyanate groups, a mixture of two or more such polyisocyanates, ora modified polyisocyanate obtainable by modifying such a polyisocyanateor a mixture.

For example, preferred is a polyisocyanate such as tolylene diisocyanate(TDI), diphenylmethane diisocyanate (MDI), polymethylenepolyphenylisocyanate, xylylene diisocyanate, isophorone diisocyanate orhexamethylene diisocyanate, or a prepolymer type modified product, anurate modified product or a urea modified product thereof.

The composition of the present invention is useful for a wide range ofapplications such as a solvent, an aerosol propellant, a refrigerant anda blowing agent. Among them, it is particularly suitable for a blowingagent for preparation of a plastic foam, particularly a blowing agentfor preparation of a polyurethane foam. When the composition of thepresent invention is used as a polyurethane blowing agent, thecomposition may contain a polyol component or an isocyanate component.

In the composition of the present invention, the content of "(i) acombination of (a) and at least member selected from (b) to (e)" or"(ii) at least one member selected from (f) and (g)" is from 0.001 to 10parts by weight per 100 parts by weight of the pentafluoropropane,preferably from 0.01 to 10 parts by weight per 100 parts by weight ofthe pentafluoropropane.

"(i) a combination of (a) and at least one member selected from (b) to(e)" and "(ii) at least one member selected from (f) and (g)" may beused in combination.

In (i), the proportions of (a) and at least one member selected from (b)to (e) are preferably such that the former is from 0.01 to 100 parts byweight and the latter is 1 part by weight.

Further, in the application as a polyurethane blowing agent, when (f) isa halogen-containing polyether polyol, such a polyether polyol usuallyconstitutes a part of a polyol component. Likewise, when (g) is areaction product of a halogen-containing polyether polyol with anisocyanate compound and has a hydroxyl group, such a reaction productusually constitutes a part of a polyol component.

Further, when (g) is a reaction product of a halogen-containingpolyether polyol with an isocyanate compound and has an isocyanategroup, such a reaction product usually constitutes a part of anisocyanate component.

The composition of the present invention may further contain otherstabilizer, for example, at least one member selected from a compoundhaving --COR³ wherein R³ is an alkyl group, a halogenated alkyl group,an aryl group or a halogenated aryl group, a compound having --CO₂ R⁴wherein R⁴ is a residue having a hydroxyl group removed from an alcoholor a halogenated alcohol, a halogenated aromatic hydrocarbon having ahalogen atom directly bonded to a carbon atom of the aromatic ring, aphenol, an unsaturated group-containing aromatic compound, ametallocene, a metal acetyl acetonate, an oxime, an epoxy compound, anorganic acid, an ammonium salt or amine salt of an organic acid, ahalogenated alkane and a halogenated alcohol, in an amount of from 0.001to 10 parts by weight, preferably from 0.01 to 10 parts by weight, per100 parts by weight of the pentafluoropropane.

The compound having COR³ wherein R³ is an alkyl group, a halogenatedalkyl group, an aryl group or a halogenated aryl group, may, forexample, be an aliphatic monoketone such as methyl ethyl ketone ormethyl isobutyl ketone, a phenone such as acetophenone,p-methylacetophenone, n-butyrophenone or benzophenone, or a β-diketonesuch as benzoylacetone, α'-benzoyl-α,α,α-trifluoroacetone,dibenzoylmethane, furoylacetone, acetylacetone or(trifluoroacetyl)acetone. Particularly preferred is an aliphaticmonoketone or a phenone.

R³ which is a halogenated alkyl group or a halogenated aryl group, ispreferably an alkyl group or an aryl group, wherein at least a part ofhydrogen atoms in the alkyl group or the aryl group is substituted by ahalogen atom such as a fluorine atom or a chlorine atom. The carbonnumber of the alkyl group or the halogenated alkyl group is preferablyfrom 1 to 5.

The compound having --CO₂ R⁴ wherein R⁴ is a residue having a hydroxylgroup removed from an alcohol or a halogenated alcohol, may, forexample, be an ester of an aliphatic carboxylic acid, such as ethylacetate, butyl acetate, amyl acetate, ethyl formate,2,2,2-trichloroethyl formate, butyl butyrate, amyl butyrate, methylpropionate, ethyl propionate, butyl propionate, amyl propionate, butylacrylate, butyl methacrylate, methyl stearate, ethyl stearate, butylstearate, butyl oleate, ethyl laurate, dimethyl oxalate, dibutylmalonate, diethyl succinate, dibutyl tartarate, methyl maleate, ethylmaleate, chloroethyl acetate, chloropropyl acetate, methyl laurate,ethyl laurate, methyl 3-oxobutanoate, ethyl 3-oxobutanoate, methylacetoacetate, ethyl acetoacetate, ethyl 3-oxopentanoate or ethyl3-oxooctadecanoate, or an ester of an aromatic carboxylic acid, such asethyl benzoate, ethyl 4-methylbenzoate, dimethyl phthalate, chloroethylbenzoate or chloropropyl benzoate.

Other esters may, for example, be esters of aliphatic carboxylic acidsor aromatic carboxylic acids with halogen-containing polyether polyolshaving a halogenated alkyl group. Such esters are preferred, since theyare excellent in stability in a mixed state of a polyol and a blowingagent. Such halogen-containing polyether polyols may be the same asdescribed above with respect to (g) or (f).

R⁴ which is a residue having a hydroxyl group removed from a halogenatedalcohol, may, for example, be a residue having a hydroxyl group removedfrom a usual halogenated alcohol having a halogenated alkyl group, or aresidue having a hydroxyl group removed from the above-mentionedhalogen-containing polyether polyol.

The halogenated alkyl group in the halogenated alcohol or thehalogenated alkyl group in the halogen-containing polyether polyol, ispreferably an alkyl group, wherein at least a part of hydrogen atoms inthe alkyl group is substituted by a halogen atom such as a fluorine atomor a chlorine atom. As the active hydrogen compound, the same activehydrogen compound as described above may be employed.

The halogenated aromatic hydrocarbon having a halogen atom directlybonded to a carbon atom of the aromatic ring, may, for example, bep-fluorotoluene. The halogen atom is preferably a halogen atom selectedfrom a fluorine atom, a chlorine atom and a bromine atom.

The phenol may be the same as the phenol in the above-described (f).

The unsaturated group-containing aromatic compound may, for example, bestyrene, vinyltoluene, α-methylstyrene, p-isopropenyltoluene,o-isopropenyltoluene, p-isopropenyl-o-xylene,p-isopropenyl-α-ethylstyrene, methoxystyrene or ethoxystyrene.

The metallocene may, for example, be ferrocene, nickelocene,cobaltocene, molybdocene dichloride, dicyclopentadienyltitaniumdichloride or dicyclopentadienylzirconium dichloride.

The metal acetyl acetonate may, for example, be copper acetyl acetonate,iron acetyl acetonate, manganese (II) acetyl acetonate or cobalt (II)acetyl acetonate.

The oxime may, for example, be acetoaldoxime, cyclohexanoneoxime,benzaldoxime or acetoxime.

The epoxy compound may, for example, be a monoepoxy compound such asethylene oxide, 1,2-butylene oxide, propylene oxide, styrene oxide,cyclohexene oxide, glycidol, epichlorohydrin, phenyl glycidyl ether,glycidyl methacrylate, allyl glycidyl ether, methyl glycidyl ether,butyl glycidyl ether or 2-ethylhexyl glycidyl ether, or a polyepoxycompound such as diepoxybutane, vinylcyclohexene dioxide, neopentylglycol diglycidyl ether, ethylene glycol diglycidyl ether, glycerolpolyglycidyl ether or trimethylolpropane triglycidyl ether.

The organic acid may, for example, be formic acid, acetic acid,propionic acid or lauric acid. The amine used for the ammonium salt orthe amine salt of this organic acid, may, for example, be dimethylamine,diethylamine, trimethylamine or triethylamine.

The halogenated alkane may, for example, be chloroethane,1-chloropropane, 2-chloropropane, 1-chlorobutane, 2-chlorobutane,bromomethane, dibromomethane, bromoform, carbon tetrabromide,bromoethane, 1-bromopropane, 2-bromopropane, 1-bromobutane,2-bromobutane, 1,2-dibromobutane, 1,3-dibromobutane, 1,4-dibromobutane,2,3-dibromobutane, iodoethane, 1-iodopropane, 2-iodopropane,1-iodobutane or 2-iodobutane.

The halogenated alcohol may, for example, be 2-chloroethanol,2,2-dichloroethanol, 2,2,2-trichloroethanol, 1-chloro-2-propanol,2-bromoethanol, 2,2-dibromoethanol, 2,2,2-tribromoethanol,ethylenechlorohydrin or propylenebromohydrin.

Now, the present invention will be described in further detail withreference to Examples and Comparative Examples. However, it should beunderstood that the present invention is by no means restricted by suchspecific Examples.

EXAMPLES 1 to 23 (the present invention), EXAMPLES 24 to 28 (ComparativeExamples), EXAMPLES 29 to 36 (the present invention) and EXAMPLE 37(Comparative Example)

Tables 2 to 4 and 6 show the results of cases wherein R245fa was used asa polyurethane blowing agent. Table 7 shows the results of cases whereinR245ca was used as a polyurethane blowing agent.

The tests in Examples 1 to 28 were carried out by using test samplesprepared by mixing predetermined amounts of the polyol component (P1liquid) as identified in Table 1, the isocyanate component (I liquid) asidentified in Table 1, blowing agent R245fa and various organiccompounds as identified in Tables 2 to 4.

Using a wooden box having a size of 200 mm×200 mm ×200 mm, apolyurethane foam was prepared from the above test sample, whereupon itscenter portion was sampled. The amount of decomposition product R1234zeor R1234ye formed by the heat generation during foaming, was analyzed bygas chromatography, whereby the effect for controlling the decompositionproduct was determined.

The "added amount" in Tables 2 to 4 means the amounts of the organiccompounds in Tables 2 to 4 added to P1 liquid. The blowing agent waspreliminarily incorporated to P1 liquid. The "added amount" in Tables 6and 7 means the amounts of the organic compounds in Tables 6 and 7 addedto P2 liquid or I liquid.

In Examples 29, 30, 33 and 34, the organic compounds were preliminarilyincorporated to P2 liquid. In Examples 31, 32, 35 and 36, the organiccompounds were preliminarily incorporated to B liquid. Further, theblowing agent was preliminarily incorporated to P2 liquid.

In Tables 6 and 7, "OH value" represents a hydroxyl value (unit:mgKOH/g), and in Tables 6 and 7, "NCO content" represents the content ofisocyanate groups (unit: wt%).

Further, in Tables 6 and 7, X represents an epichlorohydrin adductderivative of bisphenol A (OH value: 250), Y represents anepichlorohydrin adduct derivative of glycerol (OH value: 450), DEAMrepresents diethanolamine, and EPCH represents epichlorohydrin.

In Tables 2 to 4 and 6, A to D in the column for "Decomposition Product"indicate the concentrations (N ppm) of decomposition product R1234ze andhave the following meanings.

A: N<50 ppm

B: 50 ppm≦N<100 ppm

C: 100 ppm≦N<500 ppm

D: N≧500 ppm

Further, in Table 7, E and F in the column for "Decomposition Product"indicate the concentrations (M ppm) of decomposition product R1234ye andhave the following meanings.

E: M<50 ppm

F: M≧500 ppm

                  TABLE 1    ______________________________________    P1 liquid    Polyol EL-750ED (manufactured by                          100 parts by weight    Asahi Olin K.K.    Catalyst Dabco-33LV   2 parts by weight    (manufactured by Sankyo Air    Product K.K.)    Foam stabilizer SH-193                          2 parts by weight    (manufactured by Toray Silicone    K.K.)    Pure water            2 parts by weight    I liquid    Isocyanate PAPI-135   150 parts by weight    (manufactured by Mitsubishi    Kasei Dow K.K.)    Blowing agent R245fa  35 parts by weight    ______________________________________

                  TABLE 2    ______________________________________                           Added                           amount    Example                (parts by Decomposition    No.     Organic compound                           weight)   product    ______________________________________    1       Nitromethane   1.0       A            Acetonitrile   0.5    2       Nitromethane   1.0       A            Benzonitrile   0.5    3       Nitromethane   1.0       A            N,N-Dimethylacetamide                           0.5    4       Nitromethane   1.0       A            γ-Butyrolactone                           0.5    5       Nitromethane   1.0       A            p-Benzoquinone 0.5    6       Nitroethane    1.0       A            Acetonitrile   0.5    7       Nitroethane    1.0       A            Benzonitrile   0.5    8       Nitroethane    1.0       A            N,N-Dimethylacetamide                           0.5    9       Nitroethane    1.0       A            γ-Butyrolactone                           0.5    10      Nitroethane    1.0       A            p-Benzoquinone 0.5    ______________________________________

                  TABLE 3    ______________________________________                           Added                           amount    Example                (parts by Decomposition    No.     Organic compound                           weight)   product    ______________________________________    11      p-Nitrotoluene 1.0       A            Acetonitrile   0.5    12      p-Nitrotoluene 1.0       A            Benzonitrile   0.5    13      p-Nitrotoluene 1.0       A            N,N-Dimethylacetamide                           0.5    14      p-Nitrotoluene 1.0       A            γ-Butyrolactone                           0.5    15      p-Nitrotoluene 1.0       A            p-Benzoquinone 0.5    16      p-Nitrotoluene 1.0       A            Acetonitrile   0.5            p-Fluorotoluene                           0.5    17      p-Nitrotoluene 1.0       A            N,N-Dimethylacetamide                           0.5            p-Fluorotoluene                           0.5    18      p-Nitrotoluene 1.0       A            γ-Butyrolactone                           0.5            p-Fluorotoluene                           0.5    19      p-Nitrotoluene 1.0       A            p-Benzoquinone 0.5            p-Fluorotoluene                           0.5    ______________________________________

                  TABLE 4    ______________________________________                           Added                           amount    Example                (parts by Decomposition    No.     Organic compound                           weight)   product    ______________________________________    20      p-Nitrotoluene 1.0       A            Acetonitrile   0.5            Chloroethyl acetate                           0.5    21      p-Nitrotoluene 1.0       A            N,N-Dimethylacetamide                           0.5            Chloroethyl acetate                           0.5    22      p-Nitrotoluene 1.0       A            γ-Butyrolactone                           0.5            Chloroethyl acetate                           0.5    23      p-Nitrotoluene 1.0       A            p-Benzoquinone 0.5            Chloroethyl acetate                           0.5    24      p-Nitrotoluene 1.0       B    25      p-Nitrotoluene 0.5       C    26      Nitromethane   1.0       B    27      Nitroethane    1.0       B    28      Nil                      D    ______________________________________

                  TABLE 5    ______________________________________    P2 liquid    Polyol having a OH value of 450,                          100 parts by weight    having PO and EO added to m--    tolylenediamine    Polyol having a OH value of 450,                          50 parts by weight    having PO and EO added to    sucrose    Catalyst: Dabco-33LV  2 parts by weight    (manufactured by Sankyo Air    Product K.K.)    Foam stabilizer: SH-193                          2 parts by weight    (manufactured by Toray Silicone    K.K.)    Pure water            2 parts by weight    I liquid    Isocyanate: PAPI-135  150 parts by weight    (manufactured by Mitsubishi    Kasei Dow K.K.)    Blowing agent         35 parts by weight    ______________________________________

                  TABLE 6    ______________________________________                           Added                           amount    Example                (parts by Decomposition    No.     Organic compound                           weight)   product    ______________________________________    29      X (OH value: 250)                           5.0       A    30      EPCH adduct derivative                           5.0       A            of DEAM (OH value:            250)    31      TDI prepolymer of X                           5.0       A            (NCO content: 15)    32      MDI prepolymer of Y                           5.0       A            (NCO content: 22)    ______________________________________

                  TABLE 7    ______________________________________                           Added                           amount    Example                (parts by Decomposition    No.     Organic compound                           weight)   product    ______________________________________    33      X (OH value: 250)                           5.0       E    34      EPCH adduct derivative                           5.0       E            of DEAM (OH value:            250)    35      TDI prepolymer of X                           5.0       E            (NCO content: 15)    36      MDI prepolymer of Y                           5.0       E            (NCO content: 22)    37      Nil            --        F    ______________________________________

The composition of the present invention is useful as a blowing agent,an aerosol propellant, a refrigerant or a solvent, and it not only showsan excellent stabilizing effect but also exhibits a remarkable effectfor controlling formation of R1234ze or R1234ye.

What is claimed is:
 1. A fluorine-containing hydrocarbon compositioncomprising the following (1) and (2), wherein the proportions of (1) and(2) in the composition are such that (1) is 100 parts by weight, and (2)is from 0.001 to 10 parts by weight:(1) at least one pentafluoropropaneselected from 1,1,1,3,3-pentafluoropropane and1,1,2,2,3-pentafluoropropane, (2) the following (i) or (ii):(i) acombination of (a) and at least one member selected from the following(b) to (e):(a) a compound having --NO₂, (b) a compound having --CN, (c)a compound having --CONR¹ R² wherein each of R¹ and R² which areindependent of each other, is a hydrogen atom or an alkyl group, (d) alactone, (e) a quinone, (ii) at least one member selected from thefollowing (f) and (g):(f) a reaction product of a compound having ahalogen atom and an epoxy group with an active hydrogen compound, (g) areaction product of a compound having a halogen atom and a hydroxylgroup with an isocyanate compound.
 2. The composition according to claim1, wherein the proportions of (a) and at least one member selected from(b) to (e) in (i) are such that the former is from 0.01 to 100 parts byweight, and the latter is 1 part by weight.
 3. The composition accordingto claim 1, wherein the fluorine-containing hydrocarbon composition is ablowing agent for preparation of a plastic foam.
 4. The compositionaccording to claim 1, wherein (a) is a nitroalkane or an aromatic nitrocompound.
 5. The composition according to claim 1, wherein (b) is analiphatic nitrile or an aromatic nitrile.
 6. The composition accordingto claim 1, wherein (c) is a formamide or an acetamide.
 7. Thecomposition according to claim 1, wherein (d) is β-lactone, γ-lactone orδ-lactone.
 8. The composition according to claim 1, wherein (e) isp-benzoquinone, o-benzoquinone, 9,10-anthraquinone or1,4-naphthoquinone.
 9. The composition according to claim 1, wherein (f)is a halogen-containing polyether polyol.
 10. The composition accordingto claim 1, wherein the compound having a halogen atom and an epoxygroup in (f) is an aliphatic hydrocarbon having a halogen atom and anepoxy group.
 11. The composition according to claim 10, wherein thealiphatic hydrocarbon having a halogen atom and an epoxy group isepichlorohydrin.
 12. The composition according to claim 1, wherein theactive hydrogen compound in (f) is a monool, a polyol, a phenol, acompound having a primary amino group, a compound having a secondaryamino group, or a compound having a carboxyl group.
 13. The compositionaccording to claim 1, wherein (g) is a reaction product of (f) with anisocyanate compound.
 14. The composition according to claim 13, wherein(f) is a halogen-containing polyether polyol.
 15. The compositionaccording to claim 14, wherein the halogen-containing polyether polyolis a reaction product of an aliphatic hydrocarbon having a halogen atomand an epoxy group with an active hydrogen compound.
 16. The compositionaccording to claim 15, wherein the aliphatic hydrocarbon having ahalogen atom and an epoxy group is epichlorohydrin.
 17. The compositionaccording to claim 15, wherein the active hydrogen compound is a monool,a polyol, a phenol, a compound having a primary amino group, a compoundhaving a secondary amino group or a compound having a carboxyl group.18. The composition according to claim 1, wherein the isocyanatecompound in (g) is an aromatic, alicyclic or aliphatic polyisocyanate.